CN1032641C - Silica sols, a process for the preparation of silica sols and use of the sols - Google Patents

Silica sols, a process for the preparation of silica sols and use of the sols Download PDF

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CN1032641C
CN1032641C CN93117068A CN93117068A CN1032641C CN 1032641 C CN1032641 C CN 1032641C CN 93117068 A CN93117068 A CN 93117068A CN 93117068 A CN93117068 A CN 93117068A CN 1032641 C CN1032641 C CN 1032641C
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colloidal sol
value
paper
silicon dioxide
surface area
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CN1084490A (en
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A·克杰尔
L·博
L·埃里克
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HC Starck GmbH
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    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/63—Inorganic compounds
    • D21H17/67—Water-insoluble compounds, e.g. fillers, pigments
    • D21H17/68—Water-insoluble compounds, e.g. fillers, pigments siliceous, e.g. clays
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B33/00—Silicon; Compounds thereof
    • C01B33/113—Silicon oxides; Hydrates thereof
    • C01B33/12—Silica; Hydrates thereof, e.g. lepidoic silicic acid
    • C01B33/14—Colloidal silica, e.g. dispersions, gels, sols
    • C01B33/141—Preparation of hydrosols or aqueous dispersions
    • C01B33/142—Preparation of hydrosols or aqueous dispersions by acidic treatment of silicates
    • C01B33/143—Preparation of hydrosols or aqueous dispersions by acidic treatment of silicates of aqueous solutions of silicates
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B33/00—Silicon; Compounds thereof
    • C01B33/113—Silicon oxides; Hydrates thereof
    • C01B33/12—Silica; Hydrates thereof, e.g. lepidoic silicic acid
    • C01B33/14—Colloidal silica, e.g. dispersions, gels, sols
    • C01B33/146—After-treatment of sols
    • C01B33/149—Coating
    • C—CHEMISTRY; METALLURGY
    • C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12P—FERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
    • C12P21/00—Preparation of peptides or proteins
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/20—Macromolecular organic compounds
    • D21H17/33—Synthetic macromolecular compounds
    • D21H17/34—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D21H17/37—Polymers of unsaturated acids or derivatives thereof, e.g. polyacrylates
    • D21H17/375—Poly(meth)acrylamide
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/20—Macromolecular organic compounds
    • D21H17/33—Synthetic macromolecular compounds
    • D21H17/34—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D21H17/41—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing ionic groups
    • D21H17/44—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing ionic groups cationic
    • D21H17/45—Nitrogen-containing groups

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Abstract

Silica sols with a high content of microgel and particles with a specific surface area within the range 300 to 700 m<2>/g, preferably 400 to 650 m<2>/g. The sols can be prepared by acidification of a water glass solution and alkalization at a certain dry content, alternatively to a certain pH. The sols are particularly suitable for use as additives in papermaking in combination with cationic polymers and especially in combination with cationic acrylamide based polymers.

Description

Silica sols, a process for the preparation of silica sols and use of the sols
The present invention relates to novel silicon dioxide gel, be applicable to the method and this application of novel colloidal sol in paper-making process that prepare this colloidal sol.More particularly, the present invention relates to novel silicon dioxide gel, it is higher that the particle that this colloidal sol comprises has the content of so-called micro gel in certain specific surface area and this solution.Described novel colloidal sol is suitable for combining as the additive in the paper-making process with polymer phase especially.
Silicon dioxide gel (this title is used in reference to silica hydrosol in this article) is for comprising the aqueous phase system of very little silica dioxide granule, and these systems bases wherein particulate size (also according to some other factor) are applied in the various fields.In the past few years, the silica-based colloidal sol that contains very little colloid negatively charged ion silica dioxide granule is applied in the paper-making industry more and more.Here, silicon dioxide gel is with positively charged ion or the amphiphilic polymers additive as paper making raw material, and main purpose is to improve the retention value and the dehydration of material in the paper-making process.For instance, disclosed the colloidal silica sol that uses together with cationic starch in No. 41056, the European patent.In PCT application for patent WO86/00100 and WO86/05826 number, disclosed being used in combination of silicon dioxide gel (particle wherein contains aluminium at least in surface group) and positively charged ion natural polymer and cationic polyacrylamide respectively.The general introduction of these silica dioxide granules is that its specific surface area is at 50 to 1000 meters 2In/gram the scope.The colloidal sol of using in selecting paper industry belongs to following type: contain discrete colloidal solid, granular size is generally from about 4 to about 7 nanometers, that is specific surface area is from about 700 to about 300 meters 2/ gram, particularly its particulate surface-area is 500 meters 2Colloidal sol about/gram has obtained business-like application.It is generally acknowledged that its effect of the colloidal sol that particle constituted with above-mentioned size is best, and they also are suitable from stability.Following target is quite general, and promptly used silicon dioxide gel should be monodispersed as far as possible, that is to say that the particle in the colloidal sol should disperse, non-accumulative, and its size-grade distribution should be tried one's best narrower.Thereby just try hard to avoid assemble (that is avoiding forming micro gel) during colloidal sol in preparation.According to PCT application for patent WO91/07350 number, developed and had the silicon dioxide gel that micro gel to a certain degree forms.This class colloidal sol is based on the very large particle of specific surface area, and has been found that they cooperate with polymer phase and be specially adapted to select in the paper industry.Described colloidal sol is based on very big (from 750 to 1000 meters of specific surface areas 2/ gram is preferably 800 to 950 meters 2/ gram) particle, and these particles carry out surface modification with aluminium so that high surface area keeps stable.
According to the present invention, have been found that silica-based particles is (promptly based on SiO 2Particle) colloidal sol (its specific surface area is at 300 to 700 meters 2In/gram the scope, and the particulate colloidal sol with high level) fabulous effect can be provided to retention value in the paper-making process and dehydration.Particularly find, use together with polymkeric substance by the colloidal sol of the particle of given specific surface area of the present invention and micro gel content then the effect improved greatly (but silica-based sols that mainly comprise discrete particle identical with used in the past specific surface area scope compared) can be provided based on cation acrylamide if contain.The content of micro gel (or aggregate) can be controlled in the process of making colloidal sol.
Thereby the present invention relates to novel silicon dioxde solution, also relate to the method for making this colloidal sol and the application of this colloidal sol.
The novel colloidal sol of this class is characterised in that the micro gel (promptly lower S value) with high level, and its feature is that also the specific surface area of sol particle is at 300 to 700 meters 2In/gram the scope.According to Sears at " analytical chemistry " (Analytical Chemistry) the 28th volume (1956), the 12nd phase, go up the methods of introducing for 1981 to 1983 pages, by the sodium hydroxide titration with measure given specific surface area.Described specific surface area should be at 400 to 650 meters 2In/gram the scope.
With used in the paper-making industry, the known commercial colloidal sol with above-mentioned specific surface area compares, and colloidal sol of the present invention has higher micro gel content, just lower S value.It is believed that micro gel (being aggregate) exists with the two dimension or the three-dimensional structure form of accumulative primary granule to a great extent, have more or less formation as cloud form.The S value of colloidal sol of the present invention is in 15% to 40% (weight) scope, and the S value should be in 15% to 35% scope.The mensuration of given S value and method of calculation are according to Iler, R.K. and Dalton, R.L. " physical chemistry magazine " (J.Phys.Chem.) the 955th to 957 page of the 60th volume (1956) the above.The S value can be regarded as the measurement of aggregate or micro gel formation degree, and low S value representation particulate sol-fraction proportion is bigger; The S value also can be regarded as SiO in the disperse phase 2The yardstick of content (representing) with percent by weight.
Particle in the colloidal sol of the present invention can be unmodified silica dioxide granule or the silica dioxide granule of doing surperficial modification with aluminium.Contain without the colloidal sol of the silicon-dioxide of aluminium modification better.For the particle of aluminium modification, degree that should modification is 2% to 25%, with 3% to 20% for well.Aluminium modification degree is meant and has replaced the ratio of the aluminium atom of Siliciumatom in the particle surface.Aluminium modification degree is represented with per-cent, and is calculated by 8 silanol of every square nanometers.This is by Iler, and R.K. is at " colloid and interface science magazine " (Journal ofColloidal and Interface Science) the 55th volume (1976), the 1st phase, describes in the 25th to 34 page.Colloidal sol of the present invention should have by SiO 2The dried content that calculates from about about 3% to 40% (weight), dried content in about 5% to 30% (weight) scope for well.
Have been found that these novel colloidal sols that contain anion particle are applicable to the production of paper and analogous products, find that also they use and can provide good improvement to retention value and dehydration with cationic polymers.Particularly find; if of the present invention containing without the novel colloidal sol of the particulate of aluminium modification uses with the cation type polymer based on acrylamide; great improving (compare with this class colloidal sol of industrial use, this type of colloidal sol has the particle of same granularity but wherein particle all disperses basically) can be provided.In appended this patent claim the defined silicon dioxide gel, the present invention also relates to the making method of this novel silicon dioxide gel and the application of such colloidal sol described in the appended this patent claim.
The invention still further relates to and have from 300 to 700 meters of S value and the specific surface area scopes of hanging down 2The making method of silicon dioxide gel of/gram, according to the present invention, the preparation silicon dioxide gel begins from common basic metal water glass (potassium or sodium silicate, with sodium silicate for well).SiO in the water glass 2With Na 2O or K 2The mol ratio of O is by can be in 1.5: 1 to 4.5: 1 scopes known at present, should be in 2.5: 1 to 3.9: 1 scope, and Na wherein 2O and K 2Below the O all with M 2O represents.Used is the dilute solution of water glass, and this solution should contain SiO 2About 3% to about 12% (weight), with about 5% to about 10% (weight) for well.The pH value of this water glass solution is generally about 13 or more than 13, be acidified to the pH value is about about 1 to 4.Acidifying can be carried out in a known way by adding mineral acid, for example uses sulfuric acid, hydrochloric acid and phosphoric acid, perhaps also can be with other some pharmaceutical chemicals of glass acidifying that can supply water, as ammonium sulfate and carbonic acid gas.When adding mineral acid, acidifying is carried out in two steps, and the first step to pH value is about 8 to 9, subsequently further be acidified to the pH value be about 1 to 4 about before, allow certain maturation process, that is the particle growth process.But acidifying should be carried out with acid cation-exchanger, and except other factors, acid cation-exchanger can obtain more stable product and the acidic sol that contains sodium hardly is provided.Acidifying should use storng-acid cation exchange resin (for example sulfonic acid type) to carry out.It is about 2.0 to 4.0, the most suitable from about 2.2 to about 3.0 that acidifying should proceed to the pH value.And then resulting acidic sol becomes alkalescence after making acidifying.Alkalization is carried out with conventional base, as the oxyhydroxide of sodium, potassium and ammonium.Yet alkalization should realize by adding water glass.In this alkalinization step, use potassium or sodium silicate (especially sodium silicate), its SiO 2With M 2The mol ratio of O is as described below.The SiO of the water glass solution that is used for alkalizing 2Content should be about 3% to about 35% (weight) scope, with 5% to 30% (weight) scope for well.Alkalization should proceed to that the pH value is minimum to equal 7, is preferably to proceed to the pH value in 7.5 to 9 scopes.Alkalization should further proceed to SiO 2With M 2The final mol ratio of O is about 20: 1 to about 75: 1 scopes, with about 30: 1 to about 60: 1 scopes for well.In as above preparing the colloidal sol process, the degree that contains micro gel can be influenced by some approach, and can be controlled in desired than low value.Contain the influence that the micro gel degree can be subjected to salts contg, when also being prepared acidic sol and when alkalization concentration adjustment influence because in this step when the stable lower-most point (the pH value is about 5) by colloidal sol, the degree that contains micro gel can be affected.Can make the degree that contains micro gel reach required value by means of prolonging the time of fixing a point by minimum steady.Especially suitable is by regulating dry matter content (SiO when alkalization 2Content) control the degree that contains micro gel, wherein higher dry matter content causes lower S value.SiO when alkalizing by making 2Content remains in 7.5% to 5% (weight) scope, and may command S value is a set-point 15% to 40%.The another kind of proper method that control contains the micro gel degree is to regulate to be basified to certain pH value, and the pH value that is reached that alkalizes that more than provides has been controlled the S value, and the pH value is low, and then the S value is also lower.In order to obtain the colloidal sol of S value in 15% to 40% scope, alkalization pH value should be controlled at 7.5 to 8.5 scopes.When alkalization is a pH scope, suitable SiO 2Content about 5% to about 6% (weight) scope.This acidic sol contains the particle of high-specific surface area, is higher than 1000 meters 2/ gram generally is about 1300 meters 2About/gram.Begin the particle growth process after the alkalization, thereby specific surface area is reduced.Thereby to carry out growth process be to reach desired specific surface area after alkalization, can make surface-area drop to 300 to 700 meters on request by thermal treatment 2/ gram scope.Regulate time and temperature when thermal treatment, comparatively high temps is down with the short time.From practical viewpoint, should be during about half an hour be to about 24 hours in, under the temperature that is no more than about 95 ℃, heat-treat.When particle reaches desired specific surface area, can carry out if necessary the surfaces of aluminum modification to obtain in sour environment, the having particle that is better than unmodified particulate charge stability.Modifying process is the aluminium modifying function, carries out with aluminate, and available sodium aluminate or potassium, better with sodium aluminate.The aluminium modifying process of particle surface carries out with currently known methods, and proceeding to the surface modification degree as mentioned above is 2% to 25%, particularly suitable with 3% to 20%.Can prepare dry matter content according to method of the present invention is about 3% silicon dioxide gel to about 40% (weight) (can be to reach after concentrating), the colloidal sol that is generated presents splendid package stability, that is they can deposit several months and the obvious decline of specific surface area can not occur, also can not form gel.
Novel colloidal sol of the present invention is specially adapted to paper-making process.The present invention also relates to this application of this colloidal sol.As mentioning in the foreword, it is well-known using silica-based colloidal sol together at papermaking neutralizing cation polymkeric substance, and its purpose at first is to improve retention value and dehydration.The using method of silicon dioxide gel of the present invention is identical with the usage of relevant anion particle silicon dioxide gel before, and colloidal sol of the present invention uses the retention value and the dehydration that can make in the paper-making process to improve greatly with cationic polymers and amphiphilic polymers.Though can adopt the order of interpolation arbitrarily, polymkeric substance should add before colloidal sol.Described colloidal sol can be used in the whole pH value of paper-making process scope (4 to 10) and good result is all arranged.The dehydration of improving also makes the speed of paper machine to increase, and reduces in the squeezing of machine and the water yield of the required removal of drying nest, so just obtains the improved greatly paper technology of economy.Should be emphasized that especially when using with the cation acrylamide based polyalcohol, low S value colloidal sol of the present invention is compared the effect of the remarkable improvement that is had with corresponding high S value colloidal sol.
Thereby the present invention also relates to the paper technology method.Described positively charged ion or amphiphilic polymers can be natural (promptly based on carbohydrate) or synthetic.Example as suitable polymers can be mentioned cationic and amphoteric starch, cationic and both sexes guar gum.Cationic and both sexes acrylamide-based polymers, cationic polyethyleneimine, polyamidoamines amine and poly-(diallyl dimethyl ammonium muriate).The use of can using separately or interosculate of described polymkeric substance.Be suitable polymkeric substance with the cation acrylamide based polyalcohol when using with colloidal sol of the present invention.
According to the present invention, the consumption of silicon dioxide gel and polymkeric substance can change in very wide scope in paper-making process.Except that other factors, the type that this depends on paper making raw material has or not filler to exist and other condition.The colloidal sol consumption should be at least 0.01 kg/ton scope for well.Its dry matter content of colloidal sol that adds in the paper making raw material is preferably 0.1% to 5% (weight) scope.Polymer loading depends on the type of polymkeric substance and to a great extent to this desired other effect.For the synthesis type polymkeric substance, usually uses at least 0.01 kg/ton (with dried fiber and the filler that may select for use siccative amount) as benchmark calculating, the quantity that should use is 0.01 to 3 kg/ton.With 0.03 to 2 kg/ton for well.For with the carbohydrate be polymer based (as cationic starch and positively charged ion guar gum) usually consumption be at least 0.1 kg/ton (is the siccative that benchmark calculates with dried fiber and the filler that may select for use).Their consumption is preferably 0.5 to 30 kg/ton, with 1 to 15 kg/ton for well.Cationic polymers and colloidal sol (are pressed SiO 2Calculating) weight ratio generally should be at least 0.01: 1, is preferably at least 0.1: 1.The upper limit of polymer loading at first is decided by the economy consideration, with costs associated.For the lower polymkeric substance of cationic, as independent use or the cationic starch that uses with other cationic polymers, then can use very high quantity, be 100: 1 or higher until ratio, its limit depends primarily on economic reason.Concerning most of systems, cationic or amphiphilic polymers and colloidal sol (are pressed SiO 2Calculate) suitable proportion in 0.2: 1 to 100: 1 scope.Colloidal sol of the present invention certainly is used from the paper-making process with additive for paper making (as hydrophobizing agent, dry reinforcer, wet toughener etc.) commonly used.Especially suitable is to use aluminum compound with colloidal sol of the present invention and cationic polymers, can further improve retention value and dehydration because have been found that aluminide.Any known aluminum compound of paper-making process that is applicable to all can use, for example alum, many aluminum compounds, aluminate, aluminum chloride and aluminum nitrate.The consumption of aluminum compound also can change in very wide scope, should make used aluminum compound and colloidal sol (press SiO 2Calculating) weight ratio was at least 0.01: 1, and the aluminum compound here is by Al 2O 3Calculate.This ratio should be no more than 3: 1, with 0.02: 1 to 1.5: 1 scope for well.Described many aluminum compounds for example can be many aluminium muriate, many aluminium sulfates and contain many aluminum compounds of chlorine root and sulfate ion simultaneously.Also can contain other negatively charged ion beyond the chlorion in many aluminum compounds, for example from the negatively charged ion of sulfuric acid, phosphoric acid, organic acid (as citric acid and oxalic acid).
Said silicon dioxide gel and polymkeric substance can be used for producing paper from different types of fibrous Mierocrystalline cellulose paper making raw material, and paper making raw material should contain this fibrid (is benchmark with the dry material) of at least 50% (weight).Said composition for example can be used for the fiber papermaking raw material from following paper pulp: dissolving pulp (as vitriol and sulfite pulp) thermal pulp, refiner paper pulp, perhaps the ground wood pulp that obtains with hardwood and cork also can be used for the paper making raw material based on the round-robin fiber.Paper making raw material also can contain the mineral filler of common type, for example kaolin, titanium dioxide, gypsum, chalk and talcum.Terminology used here " paper " and " papermaking " not only comprise paper and manufacturing thereof certainly, also comprise the other products of the cellulose fiber of sheet or coiled material shape simultaneously, as the paper pulp sheet, and pulp board, card board kai and their making.
The present invention is described further in following examples, but these embodiment do not really want to limit the present invention.Mark and per-cent do not have narration all to refer to weight fraction and weight percent if having in addition.Embodiment 1a) to 1c)
Prepared different colloidal sol in these embodiments:
1a) contrast colloidal sol.The S value is about 53, and containing specific surface area is 500 meters 2The colloidal sol without the silica dioxide granule of aluminium modification of/gram.This colloidal sol is equivalent to the industrial colloidal sol based on No. 41056 exploitations of European patent.This colloidal sol is prepared as follows: SiO 2Content is 24.2%, SiO 2: Na 2The O weight ratio is that 3.45 1275 gram water glass restrain water with 4045 and are diluted to SiO 2Content is 5.8%.This water glass solution carries out ion-exchange in the post that is filled with storng-acid cation exchange resin (trade mark is Amberlite IR120), be diluted with water to 5.41%SiO again 2400 grams are packed in the reactor through the water glass of ion-exchanges.Under fully stirring, restrain water glass (5.8%SiO with 354.2 2SiO 2: Na 2O=3.45) be added to through in the water glass of ion-exchange.Joining day is about 15 seconds.Solution with alkalization is heated to 85 ℃ subsequently, and thermal treatment is 75 minutes under this temperature.Make the colloidal sol cooling after finishing thermal treatment.
1b) by colloidal sol of the present invention.The S value is 31, and containing specific surface area is 545 meters 2The colloidal sol of the silica dioxide granule of handling without the aluminium modification of/gram.This colloidal sol is prepared as follows:
SiO 2Content is 24.2%, Si 2O: Na 2The O ratio is that 3.45 water glass, 1625 grams restrain water with 4075 and are diluted to SiO 2Content is 6.9%.This water glass solution is at embodiment 1a) carry out ion-exchange in the described ion exchange column, be diluted to 6.49%SiO through the water glass after the ion-exchange 2The water glass of 4600 grams through ion-exchange is added in the reactor vessel.Under fully stirring, restrain water glass (6.9%SiO with 400 2SiO 2: Na 2O=3.45) join through in the water glass of ion-exchange.Solution with this alkalization is heated to 85 ℃ then, and thermal treatment is 60 minutes under this temperature.Make the colloidal sol cooling after finishing thermal treatment.
1c) by colloidal sol of the present invention.The S value is 21, and containing specific surface area is 631 meters 2The colloidal sol of the silica dioxide granule of the aluminium modification of/gram.This colloidal sol is prepared as follows:
Water glass solution (the SiO of dilution 2: Na 2O=3.4) in a pillar, carry out ion-exchange, obtain SiO 2Content is 5.36% the water glass through ion-exchange.In this solution of 4000 grams, add 80.6 gram water glass (22.2%SiO 2SiO 2: Na 2O=3.41).Joining day was about for 15 seconds.Then the solution of alkalization is heated to 75 ℃ and under this temperature, handled 120 minutes.Cool off this colloidal sol, add H then +Saturated Zeo-karb (trade mark is Amberlite IR-120), it is 7.2 that its adding quantity makes the pH value.Then filter out ion exchange resin.Restrain sodium aluminate (Al toward 3770 grams through adding 25.4 in the colloidal sol of pH value adjusting 2O 3Content is 25.5%).Before adding, sodium aluminate is with 225 gram water dilutions.To be heated to 45 ℃ through the colloidal sol that the pH value is regulated before adding sodium aluminate, the joining day of aluminate is 60 minutes.
Embodiment 2
Studied colloidal sol 1a in the paper-making process in the present embodiment) and reservation effect 1b) (retention value of fiber and filler).Used is the paper making raw material of standard, promptly based on the paper pulp of following composition: 60% bleaching betulinic acid salt+40% bleaching pine sulfate pulping, wherein be added with 30% chalk as filler, also be added with the Na of 0.3 grams per liter 2SO 410H 2O.The concentration of this paper making raw material is about 5 grams per liters, and thin component concentration is 38%, and the pH value is 8.1.
In present embodiment and following examples, all keep effect with the dynamic discharge bottle evaluation of 800 rev/mins Britt.This is a retention value testing method commonly used in the paper industry.Colloidal sol uses together with different quantity and cation acrylamide based polyalcohol (trade mark is Floerger Fp4190PG, has the cationic charge of 10% (mole), and molecular weight is about 10,000,000).In used test, the cationic polyacrylamide quantity of adding is 0.8 kg/ton, and polymkeric substance added before colloidal sol.All dosage that provide in present embodiment and following examples all are to be the siccative amount that benchmark calculates with dried fiber and the filler total amount that may select for use.The results are shown in the following table.Colloidal sol 1a) retention value contrast colloidal sol kg/ton kg/ton % colloidal sol 1b)
0.3 / 48.5
0.5 51.9
0.7 53.9
1.0 58.0
1.5 61.9
0.3 57.2
0.5 63.7
0.7 73.5
1.0 76.1
1.5 78.7
Obviously, when cation polypropylene acid amide and micro gel content of the present invention higher, the reservation effect that the silicon dioxide gel that the S value is lower can be greatly improved when using together (comparing with the effect that the lower commercial colloidal sol of micro gel content uses) with this polymkeric substance.
Embodiment 3
Estimate retention value with method same among the embodiment 2 in the present embodiment, with colloidal sol 1c by the present invention preparation) with colloidal sol d according to WO91/07350 number preparation of PCT application for patent) compare, colloidal sol d) to colloidal sol 1c) similar, its S value is 21, but its particulate specific surface area is 897 meters 2/ gram.Paper making raw material is the standard paper stock, and concentration is 5.2 grams per liters.Thin component concentration is 34%, and the pH value is 8.1.Identical among used cationic polyacrylamide and the embodiment 2, add-on is 0.8 kg/ton.
Colloidal sol 1d) colloidal sol 1c retention value contrast colloidal sol
Kg/ton kg/ton %
0.2 43.9
0.5 58.5
0.8 73.0
0.2 47.5
0.4 71.6
0.8 72.1
Obviously as seen, lower with the S value, specific surface area is that the aluminium modification sol of 600 meter 2 gram magnitude can obtain suitable with low S value but the much bigger the same good reservation effect of aluminium modification sol of granule surface area.

Claims (6)

1. silicon dioxide gel, the S value that it is characterized in that this colloidal sol is in 15% to 40% scope, and this colloidal sol contains specific surface area at 300 to 700 meters 2Silica dioxide granule in the/gram scope, described particle can be aluminium modifications or without the aluminium modification.
2. silicon dioxide gel according to claim 1, the specific surface area that it is characterized in that said silica dioxide granule is at 400 to 650 meters 2In/gram the scope.
3. silicon dioxide gel according to claim 1 and 2, the S value that it is characterized in that said colloidal sol is in 15% to 35% scope.
4. according to each described silicon dioxide gel in above every claim, it is characterized in that said silica dioxide granule is without the aluminium modification.
5. according to claim 1,2 or 3 described silicon dioxide gels, it is characterized in that described silica dioxide granule aluminium surface modification.
6. silicon dioxide gel according to claim 5 is characterized in that, described particulate modification degree is 2%-15%.
CN93117068A 1992-08-31 1993-08-30 Silica sols, a process for the preparation of silica sols and use of the sols Expired - Lifetime CN1032641C (en)

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US5603805A (en) 1997-02-18
DE69302823T2 (en) 1996-09-26
ATE138354T1 (en) 1996-06-15
ES2087767T3 (en) 1996-07-16
SE9202502D0 (en) 1992-08-31
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BR9306878A (en) 1998-12-08
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JP2787377B2 (en) 1998-08-13
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DE69302823D1 (en) 1996-06-27
AU4988193A (en) 1994-03-29
MX9305272A (en) 1994-02-28
CA2141551C (en) 2000-10-10
EP0656872A1 (en) 1995-06-14
RU2081060C1 (en) 1997-06-10
CN1084490A (en) 1994-03-30
DK0656872T3 (en) 1996-10-07
FI106851B (en) 2001-04-30
FI950622A (en) 1995-02-13
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